CN105339815A - Method for controlling the optical properties of UV filter layers - Google Patents
Method for controlling the optical properties of UV filter layers Download PDFInfo
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- CN105339815A CN105339815A CN201480034855.4A CN201480034855A CN105339815A CN 105339815 A CN105339815 A CN 105339815A CN 201480034855 A CN201480034855 A CN 201480034855A CN 105339815 A CN105339815 A CN 105339815A
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- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000003287 optical effect Effects 0.000 title abstract description 11
- 239000004904 UV filter Substances 0.000 title abstract 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 73
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 claims description 60
- 239000002184 metal Substances 0.000 claims description 60
- 238000002156 mixing Methods 0.000 claims description 35
- 125000002524 organometallic group Chemical group 0.000 claims description 25
- 239000011159 matrix material Substances 0.000 claims description 20
- 230000008859 change Effects 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 14
- 239000010410 layer Substances 0.000 description 85
- 239000002243 precursor Substances 0.000 description 25
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 230000005855 radiation Effects 0.000 description 16
- 239000012702 metal oxide precursor Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000007942 carboxylates Chemical class 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- -1 oxo carboxylic acid Chemical class 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000002612 dispersion medium Substances 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- TYEYBOSBBBHJIV-UHFFFAOYSA-N 2-oxobutanoic acid Chemical compound CCC(=O)C(O)=O TYEYBOSBBBHJIV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 1
- XUBMPLUQNSSFHO-UHFFFAOYSA-M hydrogen carbonate;tetraethylazanium Chemical compound OC([O-])=O.CC[N+](CC)(CC)CC XUBMPLUQNSSFHO-UHFFFAOYSA-M 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/28—Interference filters
- G02B5/283—Interference filters designed for the ultraviolet
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/28—Interference filters
- G02B5/289—Rugate filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Abstract
The invention relates to a method for controlling the optical properties of UV-filter layers, in particular for controlling UV-absorption properties of UV filter layers containing metal oxide, thus produced UV-filter layers and use thereof, in particular for producing electronic components.
Description
The present invention relates to the method for the optical property of control UV filtering layer, particularly control the method for the UV absorptive character of containing metal oxide UV filtering layer, consequent UV filtering layer, and uses thereof, particularly producing the purposes in electronic package.
Metal oxide layer (being transparent in visible wavelength district) be in a variety of forms used as optical layers, such as traditional optical application as in glasses or other optical glass.But, they also for electronic package as in various diode (LED, OLED), transistor, solar cell etc.In the latter, usually need protection with the impact of anti-ultraviolet radiation, because they are also especially included in the organic material of quick aging under the impact of UV radiation.Therefore, in visible wavelength district for transparent and there is the UV-absorber material that metal oxide that certain UV absorbs also is used as electronic package.In addition, some in these metal oxides also have conduction or semiconduction performance, mean that they can simultaneously as the conductor in electronic package or semiconductor.
In order to the front UV-shielding properties of some metal oxide or metal mixing oxide being combined with good conduction or semiconduction performance, current use comprises metal oxide or metal mixing oxide, the complicated production method of the optical layers of such as ITO, ZnO, IZO or IGZO.
These are method particularly, such as sputtering or chemistry or physical gas-phase deposite method (CVD-chemical vapor deposition, PVD-physical vapour deposition (PVD)).These methods can control preferably, mean can realize about optical property and the desirable characteristics about electric conductivity.But CVD and PVD method is complicated in equipment, and can not operate at ambient pressure.In sputtering method, the composition of layer to be generated is determined by preassigned sputtering target and can not control in a variable manner.
In addition, metal oxide layer is also obtained by acid-or base catalysis sol-gel process usually.But the shortcoming of the method is that colloidal sol used usually only has the extremely short life-span and constantly progressively changes between the storage life under constant-quality, this means that industrial mass production is difficult to control.
All described methods have this shortcoming usually: the method does not allow the larger change of the composition of resultant layer.But the material composition of each layer also determines its optics behavior, means also there is not possible change in this respect, particularly about UV absorbance log.In addition, advantageously can obtain simply can holding manageable application process, described method is suitable for a large amount of production, at ambient pressure and work under standard atmosphere and only need low equipment complexity.
Therefore, need the straightforward procedure be applied to by metal oxide layer in matrix, the optical property in its middle level, particularly UV absorptive character can require to mate with respective application individually, the material composition of layer can change as required, and the conduction be wherein simultaneously present in metal oxide layer or semiconduction performance do not meet with quantitative adverse effect.
Therefore, the object of this invention is to provide the method for the UV absorptive character controlling containing metal oxide layer, described method is suitable for a large amount of production and meets the above-mentioned requirements of UV filtering layer by it.
Another object of the present invention is to provide and to produce by described method and the metal oxide layer of its optical property can be adjusted in a variable manner.
In addition, the object of the invention is to the purposes of the metal oxide layer showing to produce in this way.
Surprisingly, present discovery above-mentioned purpose of the present invention is realized by simple wet chemical method, wherein being applied to by organometallics in matrix and changing into metal oxide or metal mixing oxide, wherein application conditions changes and depends on that respective change obtains the different UV absorptive character of resultant layer.
Therefore, object of the present invention is realized by the method for the UV absorptive character controlling containing metal oxide UV filtering layer, wherein:
A) layer comprising organometallics to be applied in matrix and at the temperature of >230 DEG C to 500 DEG C, to change into the layer comprising metal oxide or metal mixing oxide, and/or
B) organometallics to be applied in matrix and to change into metal oxide or metal mixing oxide, and wherein apply and transform and carry out repeatedly continuously, form the multilayer system comprising metal oxide and/or metal mixing oxide simultaneously, and apply with the solution or dispersion that comprise certain density described compound for the organometallics of individual course, described concentration increases along with the layer sum in multilayer system and reduces, and the concentration wherein in each individual course is identical in single multilayer system.
In addition, object of the present invention is also realized by the containing metal oxide filtering layer produced by described method.
In addition, object of the present invention is also realized by the containing metal oxide UV filtering layer produced according to the invention purposes as the semi-conductive layer in UV filtering layer and electronic package.
According to the present invention, UV-thinks uptake zone the wavelength coverage of the incident light radiation of 200-400nm.By definition, the wavelength coverage of 100-200nm (100-280nm, UV-C radiation) also belongs to UV radiation.But the natural radiation in 100-280nm wavelength coverage is absorbed in an atmosphere substantially completely, mean that the research about the light absorption in 100-200nm wavelength coverage is unrelated to the invention.
According to the present invention, the production of UV absorbing agent and simultaneously semiconduction or conductive metal oxide layer is by being dissolved in solvent or its Organometallic precursor compounds be scattered in liquid dispersion medium carries out, namely undertaken by metal oxide precursor solution or metal oxide precursor dispersion, it can change into quite simply and can be used for the standard application of large-lot production and the coating composition of printing process or printing-ink.
Although UV absorbing agent, the many known Organometallic precursor compounds of semiconduction or conducting metal oxide (namely resolves into volatile constituent as carbon dioxide when process subsequently, the organometallics of acetone etc. and required metal oxide, described process is hot and/or undertaken by actinic radiation (UV and/or IR)) be suitable for the inventive method, for the present invention, preferred use organometallics (it is the metal carboxylate complex of metallic zinc or tin), it optionally mixes with metal carboxylate complex's (having coordination number 3-6 and each at least one part from the group of Alkoximino carboxylic acid (oximate) self-contained) of indium metal and/or gallium, or mix with the metal complex of enolate ligands with described metal, wherein term " metal " means the above-mentioned element can with metal or semimetal or transition metal performance according to the present invention.But also can use the acetate of described metal, it also easily can change into metal oxide.
Particularly preferably use the described metal carboxylate complex of at least two kinds of different metals in those or the potpourri of metal enolate compound.
Especially, at least one part is 2-(methoxyimino) alkanoate, 2-(ethoxy imino) alkanoate or 2-(oxyimino) alkanoate, and it is hereinafter also referred to as oximate.These parts are by the condensation and synthesizing in the presence of base in moisture or methanol solution of 2-ketoacid or oxo carboxylic acid and azanol or alkyl hydroxylamine.
Part used is also preferably enolate, particularly acetylacetonate, and it is also the form of the acetylacetonate complexes of various metals for other industrial object usually, is therefore commercially available.
All parts of metal carboxylate complex used according to the invention are preferably Alkoximino Carboxylic acid ligand, particularly above-mentioned those, or wherein Alkoximino Carboxylic acid ligand also only with H
2the complex compound of O coordination, but there is not other part in metal carboxylate complex yet.
Above-mentioned metal acetylacetonates is also preferably the complex compound removing acetylacetonate beyond the region of objective existence and also do not comprise other part.
If the organic metal oximate precursor compound of various metal is used as raw material, then advantageously all raw materials belong to identical material group, and namely in often kind of situation, oximate mixes with oximate.
The preferably used according to the invention preparation comprising the metal carboxylate complex of Alkoximino Carboxylic acid ligand has been described in detail in file WO2009/010142A2 and WO2010/078907A1.For this reason, with reference to the four corner of described file.
Generally speaking, metal oxide precursor, namely Organogallium, indium, zinc or tin complex are at room temperature reacted under the existence of alkali as tetraethyl ammonium bicarbonate or sodium bicarbonate by oxo carboxylic acid and at least one azanol or alkyl hydroxylamine, add inorganic gallium, indium, zinc or pink salt subsequently and are formed as gallium nitrate hexahydrate, anhydrous indium chloride or tin chloride pentahydrate.Oxo carboxylic acid used can be all representatives of this kind of compound.But, preferably use Oxoacetic Acid, oxopropanoic acid or ketobutyric acid.
Described organic metal metal oxide precursor compound (precursor) preferably uses with the form of dissolving or disperse according to the present invention.For this reason, they be dissolved in suitable solvent with suitable concentration or be scattered in suitable dispersion medium, in often kind of situation, described concentration must be adjusted for the number of painting method to be used and metal oxide precursor layer to be applied with composition.
Herein, suitable solvent or dispersion medium are water and/or organic solvent, such as alcohol, carboxylic acid, ester, ether, aldehyde, ketone, amine, acid amides or also have aromatic compounds.Also can use the potpourri of multiple organic solvent or dispersion medium or the potpourri of water and organic solvent or dispersion medium.
Preferably the metal carboxylate complex with Alkoximino Carboxylic acid ligand (oximate) described above is dissolved in 2-methyl cellosolve or tetrahydrofuran.
In first embodiment of the invention, first by the organometallics of dissolved form or discrete form or organometallics potpourri, namely metal oxide precursor solution or dispersion are applied in each matrix as individual layer, obtain metal oxide precursor layer, optionally be dried subsequently, then thermal transition becomes metal oxide layer, or depends on the composition of raw material, changes into metal mixing oxide layer.
Thermal treatment is carried out at the temperature of >230 DEG C to 500 DEG C.Herein, Temperature Treatment is carried out in atmosphere or under a shielding gas.
Surprisingly find with constant material composition (description see above), >230 DEG C causes the different UV absorptive character of resultant layer to the Temperature Treatment change within the scope of 500 DEG C.
Herein, UV in UV-A district (315-400nm) and UV-B district (280-315nm) absorb and UV-C radiation absorption within the scope of 200-280nm larger, then the Temperature Treatment of carrying out in said temperature range limit is higher.
The UV absorptive character of containing metal oxide layer to be generated are therefore advantageously by progressively adjusting the inversion temperature (depending on required UV absorptive character, at 250,300,350,400,450 or 500 DEG C) that metal oxide precursor or precursor mixture changed into metal oxide or metal mixing oxide and controlling.
Although metal oxide layer or metal mixing oxide layer still the UV-A radiation of transmission at least 90% and the uv b radiation of at least 75% under the inversion temperature of >230 DEG C to 350 DEG C, but at >350 DEG C to 500 DEG C, particularly under the inversion temperature of more than 450 DEG C, occur in the obvious absorption of 25%UV-A radiation and 40%UV-B radiation at the most at the most in UV-A and UV-B district.
On the contrary, when changing into the layer of containing metal oxide layer in the scope of >230 DEG C to 500 DEG C, the basic transmission completely of the incident light in visible wavelength district (400-780nm), but at least 95% degree ground transmission.This containing metal oxide layer meaning to be produced by above-mentioned material is optically transparent in visible region.
Temperature Treatment is on comprising IZO (3 × 100mg/g) indium zinc oxide) being shown in Fig. 1 of impact that absorb of the UV of 3-coating systems.Approximately uniform curve shape is demonstrated under often planting situation about the similar research of the individual layer system comprising 1 × 100mg/gIZO.
Therefore, depend on the application of equivalent layer, the metal oxide layer produced according to the present invention or the metal mixing oxide layer UV in 200nm to 400nm scope absorbs and controls by simple temperature treatment.Meanwhile, metal oxide layer is applied in corresponding matrix by simple wet chemical method and also changes into metal oxide layer in a straightforward manner.
If the metal oxide produced or semiconducting behavior particular importance in the application be intended to of metal mixing oxide layer; if then Temperature Treatment is not carried out in atmosphere; but at blanket gas, the words of carrying out under preferred nitrogen can further improve the conductance of the containing metal oxide layer of generation.
In a second embodiment of the present invention, the application of organometallics and change into metal oxide or metal mixing oxide carries out repeatedly continuously, makes often kind of situation be issued to the multilayer system of the combination comprising metal oxide, metal mixing oxide or comprise the two.Organometallics has finite concentration in the solution comprising it or dispersion, and described concentration reduces along with the sum raising of layer under often planting situation, and being namely high when the little number of plies, is low when the large number of plies.
Will at least 2 and 25 layers at the most, a preferred 2-15 layer continuous and one be applied on the other in matrix, make to be formed the multilayer system comprising 2-25 individual course.
Importantly before application comprises lower one deck of organometallics, the organometallics from each individual course is changed into metal oxide or metal mixing oxide respectively according to the present invention.To carry out this mode of this method, form smooth interface between individual course, wherein the interior zone of individual course still has specific pore rate under often planting situation.Fig. 3 shows the diagram of the density of material of individual layer IZO layer (comprising oximate precursor).Fig. 4 shows the diagram of the density of material of double-deck IZO layer (comprising oximate precursor).The IZO materials application of per unit area is determined in figs. 3 and 4 in often kind of situation.
Although the mechanism of action that these multilayer layers absorb about UV imperfectly understands, think that the porosity of individual course inside and the number of plies of raising produce the difference absorbing behavior according to the UV of gained multilayer layer of the present invention.
Organometallics changes into metal oxide or metal mixing oxide need not carry out as heat in this second embodiment of the present invention, but in addition or as heat treated alternative scheme, also by with actinic radiation, namely carry out with UV and/or IR radiation irradiation.When UV radiation, use <400nm, the wavelength of preferred 150-380nm.Can use and there is >800nm, the IR radiation of the wavelength of preferred >800 to 3000nm.This process also causes the release of the decomposition of Organometallic precursor and volatile organic constituents and optional water, and metal oxide layer or metal mixing oxide layer are retained in matrix.
Organometallics (metal oxide precursor compound) concentration in solution to be applied or dispersion is 1-10 % by weight based on the weight of solution or dispersion.Will at least 2 and at the most 25 layers be applied in matrix, make formed multilayer system.Herein by the low concentration at least 10 times of such as 1.5 % by weight, preferably to be applied to continuously for 12-20 time in matrix and to change into corresponding metal oxide or metal mixing oxide, and only the precursor solution comprising 10 % by weight organo metallic oxide precursors being applied in matrix for twice.
Like this, the multilayer system being no more than total (doing) thickness of 200nm is formed.Therefore, this multilayer system can be used as UV filtering layer, and if necessary as the semi-conductive layer with variable UV absorptive character.
Surprisingly, find along with the number of plies increases, when reducing for organometallics (metal oxide precursor) concentration in the solution of each individual course or dispersion, the UV appeared within the scope of the 200-400nm of research absorbs and significantly improves simultaneously.Absorb and the absorption of 40% incident light at the most in UV-B district although twice application of such as 10 % by weight metal oxide precursor solution to produce in UV-A district the UV of 25% at the most, same material is comprised 13 application, but when with the metal oxide precursor solution of respective concentration based on solution weight being 1.5 % by weight, can to realize in UV-A district at the most 50% and UV-B district in the UV of 80% incident light at the most absorb.Fig. 2 display density and number of layers are on the diagram of impact of multilayer system comprising IZO.
Therefore, the Organometallic precursor compounds concentration in each applicating medium and the simple change of the number of plies applied on the other can with the plain mode mated with each demand intentionally the UV adjusted within the scope of the UV of whole studied 200-400nm absorb.
In addition, the multilayer system comprising above-mentioned metal oxide or metal mixing oxide also has extraordinary semiconduction performance.These also by blanket gas atmosphere in multilayer system of the present invention, particularly can heat in addition and improve further in argon gas at the temperature of 200-300 DEG C.
About material therefor and the inventive method, second embodiment of the invention also produces in the wavelength coverage of 400-780nm substantially completely transparent, but at least 95% degree ground is transparent, i.e. the metal oxide layer of the incident light of wavelength described in transmission.
The multilayer system with the change composition in concentration described in second embodiment of the invention and optional material and the impact that may change the controllability of the UV absorptive character on UV absorption layer of being correlated with are greater than the impact of independent temperature treatment described in the first embodiment.Therefore, preferred second embodiment of the invention.
But, especially the embodiment of the present invention that preferred wherein the first and second embodiments combine mutually, namely control UV absorbs the method for the UV absorptive character of metal oxide layer, wherein organic metal metal oxide precursor converting compounds becomes metal oxide or metal mixing oxide heat to carry out, and produces the multilayer system comprising at least 2 containing metal oxide layers in addition.
For independent metal oxide layer or metal mixing oxide layer and also have each metal oxide precursor layer for the multilayer system according to second embodiment of the invention to be applied in matrix and can be undertaken by various known coating and printing process.Especially, spin coating method, knife coating procedure, silk screen painting method or spraying method or also have conventional printing process such as ink jet printing, flexographic printing, hectographic printing, slot die printing (slotdieprinting) and serigraphy be suitable for this object.Particularly preferably spin coating method and ink ejecting method herein.
Suitable matrix is solid matrix, such as glass, pottery, metal or plastics, and also has particularly flexible matrix, such as plastic foil or metal forming.Depend on application, these matrix also can use multiple material precoating.
The invention still further relates to the UV absorber coatings comprising metal oxide and/or metal mixing oxide, they are except the UV absorptive character that can adjust in a variable manner, also there is the optical transparence in visible wavelength district (VIS) and also have semiconduction performance, and being produced by the inventive method.
The Rotating fields of the UV absorption layer produced like this, material composition and layer-Thickness Ratio are described above in detail.According to above description, self-evident also have comprise pure metal oxides and metal mixing oxide and doped forms thereof about the term " metal oxide " of metal oxide multilayer layer of the present invention.
The invention still further relates to above-mentioned UV and absorb containing metal oxide layer in production electronic package, particularly produce the purposes in the semiconduction functional layer being used for these assemblies.
The electronic package herein considered is various diode particularly, such as LED and OLED, also has transistor and solar cell.
The inventive method controlling the UV absorptive character of containing metal oxide UV absorption layer causes being applied to the containing metal oxide UV absorption layer in conventional substrate under the normal pressure condition with simple wet chemical method, is therefore suitable for a large amount of productions of this UV absorption layer.Meanwhile, UV degree of absorption can require the simple change by temperature treatment and/or Rotating fields according to each application and adjust in a variable manner.In addition, the metal oxide layer produced like this and/or metal mixing oxide layer also have semiconducting behavior, and it also can be consisted of material if necessary and be adjusted by possible layer thickness variation.Therefore, the inventive method can produce in simple and cheap mode the containing metal oxide UV filtering layer depending on that application advantageously changes in composition and UV strainability in a large number, therefore causes having omnipotent as far as possible purposes in dog-cheap mode and in conjunction with the coating of UV strainability and semiconduction performance.
Following examples are intended to set forth the present invention.But they should never think determinate.For the preparation of in all compounds or component be known and commercially available, or to synthesize by known method.
Figure enumerates:
fig. 1: show and absorb the correlativity with the heating-up temperature (changing into the inversion temperature of metal mixing oxide) of precursor according to the UV of embodiment 1,3-layer IZO layer
fig. 2: show and absorb the correlativity to the number of layers in the multilayer system comprising IZO and corresponding precursor concentration according to embodiment 2, UV
fig. 3: the diagram of the density of material of IZO layer separately on the xsect being presented at layer
fig. 4: be presented on the xsect of double-deck system, the illustrated embodiment of the density of material of double-deck IZO layer:
Embodiment 1: produce metal oxide coating systems (IZO) by 10 % by weight IZO (tin indium oxide) precursor solutions based on oximate precursor
10 % by weight solution of 0.10g zinc oximate in 0.90g2-methyl cellosolve are mixed to make the mode of the mol ratio In:Zn=1.5:1 in potpourri with 10 % by weight solution of 0.10g indium oximate in 0.90g2-methyl cellosolve.This potpourri is mixed about 5 minutes equably in ultra sonic bath.If necessary, can carry out subsequently filtering (20 μm of pore sizes).Applied by the quartz substrate precursor solution of purification, the method be wherein made up of following 4 processing steps carries out three times continuously:
-by spin coating application precursor solution (30s, 2500rpm),
-at room temperature dry (10s),
-thermal treatment (4 minutes),
-be cooled to room temperature.
3 quartz substrates are applied, by the thermal treatment at various temperatures separately of described matrix in often kind of situation.Temperature is 250 DEG C, 350 DEG C or 450 DEG C.
Fig. 1 shows the absorption coefficient of each sample and the correlativity of heating-up temperature.The spectral width of transmitted light reduces along with heating-up temperature and improves, and absorbs, and the absorption particularly in UV-A and UV-B district improves along with heating-up temperature and significantly improves.
Embodiment 2: produce multi-lager semiconductor coating systems by the IZO precursor solution based on oximate precursor
Be similar to embodiment 1 and prepare x % by weight IZO precursor solution, wherein x has 1.5; 3.0; The value of 5.0 and 10.By repeating processing step described in embodiment 1 by matrix IZO precursor solution prepared in such as embodiment 1 coating, and change into IZO multilayer system continuously.The different number zone of interest separately with different precursor solution concentration are applied in each in several quartz substrate.Application is with lower floor:
The 2-coating systems of 10 % by weight solution is comprised in often kind of situation
The 4-coating systems of 5 % by weight solution is comprised in often kind of situation
The 7-coating systems of 3 % by weight solution is comprised in often kind of situation
The 13-coating systems of 1.5 % by weight solution is comprised in often kind of situation
Fig. 2 shows the correlativity of absorption coefficient and the number of plies and precursor solution concentration.Absorption in UV-A and UV-B district is then maximum along with the number of plies improves when low precursor solution concentration, and the spectral width of transmitted light reduces along with the number of plies when high precursor solution concentration and improves.
Claims (13)
1. control the method for the UV absorptive character of containing metal oxide UV filtering layer, wherein:
A) layer comprising organometallics to be applied in matrix and at the temperature of >230 DEG C to 500 DEG C, to change into the layer comprising metal oxide or metal mixing oxide, and/or
B) organometallics to be applied in matrix and to change into metal oxide or metal mixing oxide, and wherein apply and transform and carry out repeatedly continuously, form the multilayer system comprising metal oxide and/or metal mixing oxide simultaneously, and apply with the solution or dispersion that comprise certain density described organometallics for the organometallics of individual course, described concentration reduces along with the sum increase in multilayer system middle level, and the concentration wherein in each individual course is identical in single multilayer system.
2. method according to claim 1, is characterized in that organometallics is metal oximate, metal acetylacetonates and/or metal acetate.
3., according to the method for claim 1 or 2, it is characterized in that metal oxide and/or metal mixing oxide comprise at least tin or zinc.
4., according to method one or more in claim 1-3, it is characterized in that metal oxide and/or metal mixing oxide are ITO, ZnO, IZO or IGZO.
5., according to method one or more in claim 1-4, it is characterized in that comprising total layer thickness that the layer of metal oxide and/or metal mixing oxide or multilayer system have 200nm at the most.
6., according to method one or more in claim 1-5, it is characterized in that multilayer system is produced by the individual course that 2-25 comprises metal oxide and/or metal mixing oxide.
7., according to method one or more in claim 1-6, it is characterized in that the layer that obtains comprising metal oxide and/or metal mixing oxide or multilayer system, the incident light in 400nm to the 780nm wavelength coverage of its transmission at least 95%.
8. according to method one or more in claim 1-7, it is characterized in that the layer that obtains comprising metal oxide and/or metal mixing oxide or multilayer system, it absorbs the incident light in 315nm to the 400nm wavelength coverage of at the most 25%.
9. according to method one or more in claim 1-8, it is characterized in that the layer that obtains comprising metal oxide and/or metal mixing oxide or multilayer system, it absorbs the incident light in 315nm to the 400nm wavelength coverage of at the most 50%.
10. the containing metal oxide UV filtering layer by producing according to method one or more in claim 1-9.
11. containing metal oxide UV filtering layers according to claim 10, is characterized in that metal oxide and/or the metal mixing oxide of their containing element tin or zinc.
12. containing metal oxide UV filtering layers according to claim 10 are as the purposes of the UV filtering layer in electronic package.
13. purposes according to claim 12, is characterized in that electronic package is LED, OLED, transistor or solar cell.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP13003151.1 | 2013-06-20 | ||
| EP13003151 | 2013-06-20 | ||
| PCT/EP2014/001434 WO2014202178A1 (en) | 2013-06-20 | 2014-05-28 | Method for controlling the optical properties of uv filter layers |
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| CN105339815A true CN105339815A (en) | 2016-02-17 |
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| CN201480034855.4A Pending CN105339815A (en) | 2013-06-20 | 2014-05-28 | Method for controlling the optical properties of UV filter layers |
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| Country | Link |
|---|---|
| US (1) | US20160116652A1 (en) |
| EP (1) | EP3011373B1 (en) |
| CN (1) | CN105339815A (en) |
| WO (1) | WO2014202178A1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04264171A (en) * | 1991-02-18 | 1992-09-18 | Toyo Ink Mfg Co Ltd | Ultraviolet-absorbing film and film-forming composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5147125A (en) * | 1989-08-24 | 1992-09-15 | Viratec Thin Films, Inc. | Multilayer anti-reflection coating using zinc oxide to provide ultraviolet blocking |
| US6020590A (en) * | 1998-01-22 | 2000-02-01 | Ois Optical Imaging Systems, Inc. | Large area imager with UV blocking layer |
| US6426125B1 (en) * | 1999-03-17 | 2002-07-30 | General Electric Company | Multilayer article and method of making by ARC plasma deposition |
| DE102004027075A1 (en) * | 2004-06-02 | 2005-12-29 | se ma Gesellschaft für Innovationen mbH | UV-protected transparent coating, useful for technical applications and to prepare e.g. UV-protecting glasses, comprises UV-absorbing materials and transparent UV protecting layer that develops after drying on material |
| GB0613882D0 (en) * | 2006-07-12 | 2006-08-23 | Kidde Ip Holdings Ltd | Smoke detector |
| EP2111372B1 (en) * | 2006-12-21 | 2013-07-03 | E. I. Du Pont de Nemours and Company | Process for making suspensions of surface treated titanium (IV) oxides |
| DE102007043920A1 (en) | 2007-07-17 | 2009-01-22 | Merck Patent Gmbh | Functional material for printed electronic components |
| CN101952313B (en) * | 2007-11-27 | 2017-12-15 | 不列颠哥伦比亚大学 | 14 33 η antibody and its for diagnose and treatment of arthritis purposes |
| FR2928461B1 (en) * | 2008-03-10 | 2011-04-01 | Saint Gobain | TRANSPARENT SUBSTRATE HAVING ANTIREFLECTION COATING |
| DE102009004491A1 (en) | 2009-01-09 | 2010-07-15 | Merck Patent Gmbh | Functional material for printed electronic components |
| US9129801B2 (en) * | 2009-06-16 | 2015-09-08 | Basf Se | Thermally labile precursor compounds for improving the interparticulate contact sites and for filling the interstices in semiconductive metal oxide particle layers |
| US9263591B2 (en) * | 2009-12-18 | 2016-02-16 | Basf Se | Metal oxide field effect transistors on a mechanically flexible polymer substrate having a die-lectric that can be processed from solution at low temperatures |
| KR101361054B1 (en) * | 2011-09-02 | 2014-02-12 | 연세대학교 산학협력단 | A material for forming oxide thin film, a forming method for oxide thin film and a making method for a thim film transistor |
| CN103715234B (en) * | 2012-09-28 | 2016-05-04 | 财团法人工业技术研究院 | P-type metal oxide semiconductor material |
| US9755024B2 (en) * | 2013-01-24 | 2017-09-05 | Wisconsin Alumni Research Foundation | Functionalized ZnO or ZnO alloy films exhibiting high electron mobility |
| US20150380561A1 (en) * | 2013-03-01 | 2015-12-31 | Applied Materials, Inc. | Metal oxide tft stability improvement |
-
2014
- 2014-05-28 EP EP14750438.5A patent/EP3011373B1/en not_active Not-in-force
- 2014-05-28 US US14/898,507 patent/US20160116652A1/en not_active Abandoned
- 2014-05-28 CN CN201480034855.4A patent/CN105339815A/en active Pending
- 2014-05-28 WO PCT/EP2014/001434 patent/WO2014202178A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04264171A (en) * | 1991-02-18 | 1992-09-18 | Toyo Ink Mfg Co Ltd | Ultraviolet-absorbing film and film-forming composition |
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| WO2014202178A1 (en) | 2014-12-24 |
| EP3011373B1 (en) | 2017-11-15 |
| US20160116652A1 (en) | 2016-04-28 |
| EP3011373A1 (en) | 2016-04-27 |
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